Confinement Effects on Chemical Equilibria: Pentacyano(Pyrazine)Ferrate(II) Stability Changes within Nanosized Droplets of Water.

Nanoscale confinement is known to impact properties of molecules and we observed changes in the reactivity of an iron coordination complex, pentacyano(pyrazine)ferrate(II). The confinement of two coordination complexes in a sodium AOT/isooctane reverse micellar (RM) water droplet was found to dramatically increase the hydrolysis rate of [Fe(CN)₅pyz]3- and change the monomer-dimer equilibria between [Fe(CN)₅pyz]3- and [Fe₂(CN)10pyz]6-. Combined UV-Vis and ¹H-NMR spectra of these complexes in RMs were analyzed and the position of the monomer-dimer equilibrium and the relative reaction times were determined at three different RM sizes. The data show that the hydrolysis rates (loss of pyrazine) are dramatically enhanced in RMs over bulk water and increase as the size of the RM decreases. Likewise, the monomer-dimer equilibrium changes to favor the formation of dimer as the RM size decreases. We conclude that the effects of the [Fe(CN)₅pyz]3- stability is related to its solvation within the RM.